Hydrocarbon conversion process and catalyst therefor



United States Patent ()ffice 3,216,923 Patented Nov. 9, 1965 3,216,923 HYDROCARBON CONVERSION PROCESS AND CATALYST THEREFOR Vladimir Haensel, Hinsdale, Ill., assignor to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Filed June 29, 1964, Ser. No. 379,032 6 Claims. (Cl. 208139) The present application is a continuation-in-part of my copending application, Serial Number 107,344, filed May 3, 1961, now abandoned, which application is in turn a continuation-in-part of my copending application, Serial Number 59,176, filed September 29, 1960, and now abandoned, all the teachings of which copending applications are incorporated herein by specific reference thereto.

The present invention relates to a process for the catalytic conversion of hydrocarbons and various hydrocarbon fractions and distillates, and is specifically directed toward the conversion of hydrocarbon charge stocks containing hydrocarbons which boil at a temperature above the normal gasoline boiling range, is designated to con- F., through the utilization of a particular catalytic composite. The catalyst promoting the reactions encompassed by the present catalytic reforming process is a composite of a fluoride-free refractory inorganic oxide, a platinum-group metallic component and combined chloride, the latter being the sole halogen component of the catalyst.

In the present specification and appended claims, the phrase, hydrocarbons boiling at a temperature within the normal gasoline boiling range, is designated to connote those hydrocarbons which have normal boiling points, at standard conditions, within the range of from about 70 F. to about 400 F., as determined in :accordance with ASTM distillation method D-86-5 6. The term is specifically intended to include butanes, iso-pentane and normal pentane, straight-chain and branched-chained parafiinic hydrocarbons, aromatic hydrocarbons, and olefinic hydrocarbons boiling below a temperature of about 400 F. The term, hydrocarbons boiling at a temperature above the normal gasoline boiling range, refers, therefore, to those hydrocarbons having normal boiling points above about 400 F. My invention is particularly adaptable to the catalytic conversion of various hydrocarbon mixtures and/or hydrocarbon distillates including, but not by way of limitation, light naphthas having an initial boiling point of about 200 F. and an end boiling point of about 450 F., heavy naphthas having an initial boiling point of about 350 F. and an end boiling point of about 475 F., kerosene fractions having an initial boiling point of about 350 F. and an end boiling point as high as about 525 F. and various light and heavy gas oils, distillates, etc., having normal mid-boiling points of about 400 F., or more. The mid-boiling point is that temperature at which 50% by volume of the hydrocarbon, being distilled in accordance with ASTM method D8656, is recovered.

Developments with respect to the internal combustion engine, coupled with the ever-increasing utilization of high compression ratios therein, have resulted in a steadily increasing demand for large quantities of motor fuel possessing unusually high anti-knock characteristics, or as commonly paraphrased, :a high octane rating. This demand has necessitated the development of new and varied processes, and of substantial improvements to old, wellknown processes, having the primary purpose of producing the required quantity of motor fuel possessing the necessary quality. Various catalytic reforming processes have been developed which are capable of producing the required volumetric yield of a high octane product. These reforming processes encompass a multitude of reactions among which are hydrogenation, cyclization, cracking, dehydrogenation, alkylation, hydrocracking and isomerization. In particular instances, and under certain specified conditions of operation, the catalytic reforming process may be tailored to effect a single reaction, or a particular combination of two or more of the aforementioned reactions. Essentially, however, the process is designed for the specific purpose of converting straight-run and cracked gasoline and naphthas, having end boiling points below about 400 E, into hydrocarbon mixtures boiling within the gasoline boiling range and exhibiting a significantly higher octane rating.

An early process, thermal cracking, has been of advantage in converting heavier-than-gasoline hydrocarbons into :a useful motor fuel product. This process has, however, inherent limitations as to the maximum obtainable octane rating, and the over-all volumetric yield of liquid product processing a sufliciently high octane rating. As the octane rating of the final product is increased, the normally low volumetric yield of such product is decreased further, and the process becomes exceedingly uneconomical. Catalytic cracking, a process which utilizes an acid-acting, siliceous catalyst, is a more common method presently employed to elfect the conversion of heavier hydrocarbon charge stocks. Although the gasoline produced by catalytic cracking has a relatively high research octane number, the presence of unsaturated, olefinic hydrocarbons in large quantities, induces a detrimental effect upon road performance, and, in many instances, inhibitsthe use thereof as a motor fuel. The gasoline produced in accordance with the process of the present invention is essentially free from olefinic hydrocarbons, that is, the final product does not contain more than a few volume percent of olefins, notwithstanding the heavy character of the original hydrocarbon charge stock, and is not, therefore, degraded from the standpoint of road performance.

Another commercial process, designed to alleviate the existing situation of an over-abundance of hydrocarbons heavier than gasoline, is the process of hydrocracking, or,

as commonly designated, destructive hydrogenation. This process is diiferentiated from the siliceous-catalyst cracking process through the utilization of catalysts which generally comprise one or more active metallic components. The primary function of the hydrocracking process is to effect the cracking or splitting of carbon to carbon bon-ds while saturating the final product with added hydrogen. The hydrocracking process is most advantageous when processing hydrocarbon charge stocks boiling at a temperature above the normal middle-distillate boiling range; that is, in excess of about 600 F. to about 650 F.

The tendency of the hydrocracking process is, when proc-' essing light and heavy naphthas, and kerosene fractions, to consume aromatic hydrocarbons either through the hydrogenation thereof to naphthenes of inferior octane rating, or by the ring-opening thereof whereby paraffins are produced. The production of low boiling aromatic compounds is essential to the procurement of a high octane final product, and must result through the conversion of the available ring compounds, and open-chain hydrocarbons, without the undue destruction of either compound, or of the aromatic hydrocarbons resulting therefrom.

The object of the present invention is to provide a process for the catalytic conversion of a hydrocarbon charge stock containing hydrocarbons boiling in excess of the normal gasoline boiling range, which charge stocks are characterized by various terms, including light naphthas, heavy naphthas, kerosene fractions, etc.

In a broad embodiment, the present invention relates to a process for the reforming of a hydrocarbon charge containing hydrocarbons boiling at a temperature above the normal gasoline boiling range, which process comprises contacting said charge with a fluoride-free catalytic composite of a platinum-group metallic component, a refractory inorganic oxide and combined chloride in an amount in excess of about 0.75% by weight, calculated as elemental chlorine, at reforming conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge.

In another embodiment, the present invention involves a process for the conversion of a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above about 400 F., which process comprises reacting said charge stock with hydrogen in contact with a fluoridefree catalytic composite of a platinum-group metallic component, a refractory inorganic oxide and combined chloride in an amount above about 0.75% but below 1.5% by weight, calculated as elemental chlorine, at conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge, and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F.

A more limited embodiment of the present invention is directed toward a process for the conversion of a hydrocarbon charge containing hydrocarbons boiling at a temperature above about 400 E, which process comprises reacting said hydrocarbon charge stock with hydrogen in contact with a fluoride-free catalytic composite of alumina, from about 0.01% to about 5.0% by weight of platinum and combined chloride in an amount within the range of from about 0.75 to about 1.5% by weight, calculated as elemental chlorine, at conditions of a temperature within the range of from about 850 F. to about 1050 F., a pressure of from about 450 to about 900 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10.0, said conditions selected to produce a net volumetric yield of the hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F.

In order for a catalytic reforming process to enjoy commercial acceptance, it is extremely essential that the particular catalyst employed therein exhibits a high degree of activity, as well as the prolonged capability to perform its intended function. For example, the catalytic reforming of hydrocarbons and mixtures and hydrocarbons involves three major reactions in addition to other concommitant reactions occurring to a somewhat lesser extent. In a process for the catalytic reforming of hydrocarbons, the primary object is to dehydrogenate the naphthenic hydrocarbons to produce aromatics, to dehydrocyclicize the straight-chain paraffinic hydrocarbons to form aromatics, and to effect a controlled degree of hydrocracking which is selective both with respect to the quality and quantity thereof. Also, occurring, but to a lesser extent, are various reactions such as isomerization, hydrogen transfer, disproportionation, etc. A successful catalytic reforming process is one which effects a proper balance among these reactions, and is dependent to a great extent upon the particular catalytic composite employed to promote the various reactions.

Relatively recent developments within the petroleum industry, in regard to catalytic reforming processes, have indicated that such processes are more advantageously elfected through the untlization of a catalytic composite comprising at least one platinum-group metallic component, which composite effects the desired balance among the above-described reactions. Although the prior art abounds in a multitude of such catalytic composites, and the methods employed for the manufacture thereof, the precise mechanism of catalysis, in regard to particular reactions, is not fully understood, and the ultimate results of any process which utilizes a specific catalyst are difficult to predict with accuracy. Therefore, notwithstanding that it may be expected that a catalyst exists which best suits a given reaction, it cannot likewise be stated that a particularly selected catalyst will effect the most advantageous results when applied to a given reaction. In addition, various manufacturing procedures have been instituted for the purpose of enhancing the degree of activity and stability possessed by a given catalytic composite. In my application, Serial No. 59,176, I have described a particular catalytic composite for utilization in the reforming of hydrocarbonaceous material, and a particular method for the manufacture of the same. This catalytic composite is especially preferred for utilization in the catalytic conversion process of the present invention. I have now found that a fluoride-free catalytic composite of a platinum-group metallic component, a refractory inorganic oxide and combined chloride in an amount above about 0.75% by weight, calculated as elemental chlorine, offers unexpected advantages to the processing of hydrocarbon charge stocks containing hydrocarbons boiling above the normal gasoline boiling range, or above a temperature of about 400 F. It is recognized that the prior art, relating to the reforming of hydrocarbons is replete with descriptions of a multitude of Group VIII metal-containing catalysts for utilization therein, and further that the halogen component thereof may be selected from the group of fluorine, chlorine, bromine, and iodine. It is generally acknowledged, within the prior art, that the use of halogen, in some combined form, with the other components of the catalytic composite imparts a particular acid-acting function to the catalyst, whereby the same exhibits the propensity to be selective in the quality and quantity of hydrocracking which is effected. For the most part, the various members of the halogen family are said to be equivalent, and it is especially acknowledged that fluorine, chlorine, and mixtures thereof, are substantially equivalent for this purpose, and in many instances, fluorine is preferred. To the contrary, I have now found that the members of the halogen family are not, in fact, equivalent and further that there appears to be a certain degree of criticality attached to the concentration of combined halogen within the catalyst, and that the same unexpectedly permits the processing of those hydrocarbons exhibiting normal boiling points above about 400 F., or in excess of the normal gasoline boiling range. The prior art reforming processes, utilizing catalytic composites comprising platinum-group metallic components, are restrictive in the type of hydrocarbonaceous material which may be converted thereby. That is to say, the prior art processes for catalytic reforming to produce high octane motor fuel and/or aromatic concentrates (benzene, toluene and Xylene), restrict the charge stocks to gasoline boiling range naphthas, or hydrocarbons boiling below a temperature of 400 F. In many instances, in order to insure only gasoline boiling range hydrocarbons, the fresh charge stock will be fractionated at a cut-point of about 380 F. to about 390 F., only those hydrocarbons boiling below this level being charged to the unit. This is done to prevent prematurely rapid carbon laydown, resulting from the inclusion of the heavier hydrocarbons, and such that the latter will not interfere with the desired balance among the reactions being effected. The fluoride-free catalytic composite is not restrictive in this manner, and unexpectedly permits processing these heavier hydrocarbon components, boiling above 400 F., thereby filling the void between the catalytic reforming and cracking processes of the prior art. The particular member of the halogen family employed as an active component of the reforming catalyst is extremely important from the standpoint of imparting a high degree of activity to the catalyst, and particularly the required stability when effecting the conversion of those hydrocarbons boiling above the normal gasoline boiling range. As hereinafter indicated, fluorine is not equivalent to chlorine, and the exclusion of fluorine, coupled with a particular method of manufacture, results in a catalyst having a degree of activity and stability (the capability to function for an extended period of time) which have heretofore not been obtained by reforming catalysts when the charge stock being processed contains heavier-than-gasoline hydrocarbons. Furthermore, the inclusion of hydrocarbons boiling above 400 B, when utilizing the fluoride-free catalytic composite, does not interfere with the production of a high quality gasoline boiling range product. An unexpected result occurs with respect to the portion of the final product boiling above the gasoline boiling range, in that there is effected an increase in polynuclear aromatic hydrocarbons.

The process of the present invention utilizes a catalyst containing a platinum-group metallic component; although the process of the present invention is specifically directed to the utilization of platinum, it is intended to include other platinum-group metals such as palladium, rhodium, ruthenium, osmium, and iridium. The platinum-group metallic component, such as platinum, may exist Within the final catalytic composite, as the halide, oxyhalide, oxide, sulfide, etc., or other combined form. It is understood that the benefits afforded the processes utilizing different catalytically active metallic components are not equivalent, and that the effects of employing the method of the present invention with a particular metallic component or mixture of metallic components, or a mixture of various compounds thereof, are not necessarily the same effects observed with respect to other metallic components or mixtures of metallic components. Generally, the amount of the metallic component composited with the catalyst is small compared to the quantities of the other components combined therewith. For example, platinum and/or palladium or other metals from the platinum-group, will generally comprise from about 0.01% to about 5.0% by weight of the total catalytic composite, and more often from about 0.1% to about 2.0% by weight. The utilization of other metallic components, with or without platinum, is dependent upon the use for which the particular catalyst is intended. In any case, however, the concentration of the metallic components will be small, and will generally be within the range of from about 0.01% to about 5.0% by weight of the total catalytic composite.

Whatever the metallic component, it is usually composited with a highly refractory inorganic oxide such as alumina, silica, zirconia, magnesia, boria, thoria, titania, strontia, hafnia, etc., and mixtures of two or more including silica-alumina, alumina-boria, silica-magnesia, silica-alumina-zirconia, etc. These refractory inorganic oxides may be synthetically-prepared by any Well-known convenient method, or they may be naturally-occurring substances such as clays, sands or earths, and may be purified or activated by special treatment. Since the process of the present invention is designed to produce a net volumetric yield of hydrocarbons boiling below 0 the gasoline boiling range, a major proportion of which gasoline boiling range hydrocarbons are aromatic hydrocarbons having high octane values, and further, to result in a net volumetric increase of polynuclear aromatic hydrocarbons boiling above the normal gasoline boiling range, accompanied by a net production of hydrogen, the catalyst utilizes alumina as the carrier material, particularly avoiding those refractory inorganic oxides which tend to promote reactions which lead to the destruction of aromatic hydrocarbons. Thus, the preferred catalytic composite for utilization in the catalytic reforming process of the present invention will comprise platinum composited with alumina, the sole halogen component thereof being combined chloride in an amount within the range of from about 0.75% to about 1.5% by weight, calculated as elemental chlorine. It is understood that equivalent results are not obtained through the use of catalysts comprising varying quantities of different combinations of the metallic component hereinabove set forth. The object of the present invention has imposed certain necessary limitations and the purpose of these limitations can be defeated through the negligent utilization of a catalyst containing components detrimental thereto.

In the present specification and the appended claims, the term alumina is employed to mean porous aluminum oxide in all states of oxidation and hydration, as well as aluminum hydroxide. The alumina, employed as the carrier material for the other catalytically active metallic components, may be synthetically-prepared 0r naturally-occurring, and may be of the crystalline or gel type. Whatever type of alumina is employed, it may be activated prior to use by one or more treatments including drying, calcining, steam, etc. It may be in a form known as activated alumina, activated alumina of commerce, porous alumina, alumina gel, etc. The various types of alumina are known by many names, and it is intended to include all such types. In one of the more limited embodiments, directed toward the method of manufacturing the catalytic composite for use in the reforming process of the present invention, the alumina is synthetically prepared and subjected to a particular calcination procedure employed to facilitate the deposition of platinum and combined chloride therewith.

The alumina carrier material may be prepared by adding a suitable alkaline reagent, such as ammonium hydroxide, to a salt of aluminum such as aluminum chloride, aluminum nitrate, etc., in an amount to form aluminum hydroxide which, upon drying, is converted to alumina. The alumina may be formed into any desired shape such as spheres, pills, cakes, extrudates, powder, granules, etc. A particularly preferred form of alumina is the sphere, and alumina spheres may be continuously manufactured by the well-known oil drop method which comprises passing droplets of an alumina hydrosol into an oil bath maintained at an elevated temperature retaining the droplets in said oil bath until they set to firm hydrogel spheroids. The spheres are continuously withdrawn from the oil bath and immediately thereafter subjected to specific aging treatments, in oil and ammoniacal solutions, to impart certain desired physical characteristics thereto. Following a drying procedure, at a temperature of about 200 F. to about 400 F., to remove the greater proportion of excess moisture therefrom, the spheres are subjected to a specific, particularly preferred calcination procedure which appears to result in surface and structure characteristics which render the alumina more susceptible to the thorough penetration and more permanent deposition of the other catalytic components. The dried alumina is calcined initially at a temperature of from about 850 F. to about 1050 F. for a period of at least about one hour, and thereafter at an elevated temperature of about 1100 F. to about 1400 F., and for a time sufficient to decrease the volatile matter content of the calcined alumina to a level below about 2.0% by weight.

With respect to the catalysts comprising a platinumgroup metallic component and halogen, the prior art teaches that the halogen is generally composited with the catalyst in concentrations of from about 0.01% to about 8.0% by weight of the total catalytic composite and that such halogen may be either fluorine, chlorine, iodine, bromine, or mixtures of the same. It would appear that fluorine is less easily removed from the catalytic composite during the manufacture thereof, and further during the process in which the catalyst is employed; for this reason, it is generally stated that fluorine, or a mixture of chlorine and fluorine, is preferred. To the contrary, I have found that the halogen may be composited in such a manner that it is not easily removed from the catalyst during processing, and further that benefits are afforded the process of reforming hydrocarbons boiling above the normal gasoline boiling range when such halogen consists solely of combined chloride.

The chloride may be added to the carrier material in any suitable manner, and either before, or after the addition of the catalytically active metallic components, or simultaneously therewith. The chloride may be added as an aqueous solution of hydrogen chloride, as aluminum chloride, or through the utilization of a volatile salt such as ammonium chloride. At least a portion of the chloride may be composited with the alumina during the impregnation of the latter with the catalytically active metallic component, for example, through the utilization of chloroplatinic acid, chloroplatinous acid, etc. The primary feature of the method employed for preparing the reforming catalyst, is the treatment of the carrier material following the deposition of chloride. As in the preparation of the alumina, this particular treatment is primarily concerned with the method by which the composite is subjected to a calcination procedure. Thus, the composite is oxidized, or calcined, initially at a temperature within the range of from about 400 F. to about 600 F. for a period of at least one hour, until the volatile matter content there of is decreased to a level below about 5.0% by weight. The calcination temperature is then increased to a level within the range of about 700 F. to about 1000 F., and the composite further calcined at the elevated temperature for an additional period of at least about one hour, until the volatile matter content of the final catalytic composite is decreased to a level below about 2.0% by weight.

Although the precise eflect of this particular calcination treatment is not accurately known, it is believed that the greater proportion of the chlorine component is caused to combine with the alumina and the platinum-group metallic component in such a manner that it is not easily removed from the catalyst. Generally, reforming catalysts of this type are manufactured to contain about 0.35% by weight of combined chloride and about 0.35% by weight of combined fluoride, calculated as the elements thereof. Following the period of operation, during which the catalyst is subjected to contact with a liquid charge under elevated temperature and pressure, it is found that the greater proportion of the chlorine component has been removed. Several disadvantages inherently result after the chlorine component has been removed from the catalyst, and also appear to be inherent when the catalytic composite originally contains only fluorine as the halogen component. The fluorine component results in a greaterdegree of undesirable hydrocracking in the presence of water in amounts as low as about 10 p.p.m., and further appears to be more sensitive to the severe conditions encountered when operating at elevated temperatures and pressures; chlorine does not exhibit hydrocracking tendencies in the presence of water to as great a degree. In accordance with the catalyst manufacturing procedure hereinafter set forth, the reforming catalyst has composited therewith combined chloride in an amount of from about 0.75% to about 1.5% by weight, calculated as elemental chlorine, and being the sole halogen component of the catalytic composite. As hereinafter indicated, this catalyst has an unusually high degree of activity and the necessary stability to function acceptably for an extended period of time. An unexpected result of the relatively high chlorine-containing catalyst is that the catalyst appears to be extremely selec tive in the quality and quantity of hydrocracking which is effected. This particular propensity of catalyst is even more pronounced when the charge stock being processed contains hydrocarbons which boil at temperatures above the normal gasoline boiling range. Such a characteristic obviously results in a greater increase in the volumetric yield of normally liquid, debutanized product effluent. Furthermore, as hereinbefore set forth, and as hereinafter indicated by specific example, the all-chloride catalyst produces a liquid product in which there has been a net volumetric yield of polynuclear aromatics boiling at temperatures above about 400 F. The reactions producing this result are not expected to occur when the primary function is to obtain volumetric yields of hydrocarbons boiling below the initial boiling point of the charge stock. That is to say, the reactions accompanying these results are virtually opposed to each other, and it would not be expected that such results could be achieved simultaneously. To the contrary, it would be expected that any polynuclear aromatics originally present in the charge stock might suffer from ring opening to produce olefins and paraffins, or at least become saturated to naphthenic hydrocarbons.

Although the precise means by which the platinum component, or other platinum-group metallic component is incorporated with the other components of the catalyst, is not known, it is believed that the platinum exists in some physical association or as a chemical complex therewith. Thus, the platinum-group metal may be present as such, or as a chemical compound or in physical association with the alumina or with the other catalytically active metallic components, or in some combination with both. It is, however, believed, that the chlorine, the platinum-group metallic component and the refractory inorganic oxide, such as alumina, exists in the form of a complex compound. The method of preparing the catalyst of the pres ent invention is facilitated through the utilization of watersoluble compounds of the platinum-group metals, with which the carrier material is combined via an impregnating technique. Therefore, where the platinum group metal is platinum, it may be added to the carrier material by commingling the latter with an aqueous solution of chloroplatinic acid. Other water-soluble compounds of platinum may be employed within the impregnating solution, and include ammonium chloroplatinate, platinous chloride, platinic chloride, dinitritodiamino-platinum, etc. The utilization of a platinum-chlorine compound, such as chloroplatinic acid, is preferred since it facilitates the incorporation of both the platinum component and at least a minor quantity of the chlorine component in a single step. Hydrochloric acid may be employed in admixture with the chloroplatinic acid, to incorporate the requisite quantity of combined chloride. Following the impregnation technique, the carrier material is dried and subjected to the high-temperature calcination, or oxidation technique, as hereinbefore set forth.

Briefly, the method of manufacturing the catalytic composite, for utilization in the reforming process of the present invention, commences with the preparation of the refractory inorganic oxide carrier material, which material is preferably alumina. The particularly preferred form of alumina is the sphere, and alumina spheres may be continuously manufactured by the well-known oil drop method. This method is described in great detail in US. Patent No. 2,620,314 issued to James Hoekstra. Following the formation of the alumina spheres, and the subsequent drying thereof to remove excessive physically-held water resulting from the various steps of the sphere formation procedure, the dried spheres are subjected to high temperature calcination initially at an elevated temperature of from about 850 F. to about 1050 F. This initial calcination procedure is effected for a period of at least about one hour, after which the temperature is increased to a level of about 1100 F. to about 1400 F., at which increased temperature the spherical alumina particles are further calcined until the volatile matter content thereof is decreased to a level below about 2.0% by weight. The calcined spheres are then intimately commingled with an aqueous solution of a platinum-chlorine compound, such as chloroplatinic acid, the latter being employed in an amount to result in a final catalytic composite comprising from about 0.01% to about 5.0% by weight of platinum. After the impregnated catalyst has been dried at a relatively low temperature to remove excessive water therefrom, the temperature is increased to a level within the range of about 400 F. to about 600 F., and the composite is oxidized, or calcined, at this temperature for a time sufficient to decrease the volatile matter content thereof to a level below about 5.0% by weight. The calcination temperature is increased to a higher level within the range of about 700 F. to about 1000 F., and the procedure continued for a time sufficient to further decrease the volatile matter content to a level below about 2.0% by weight. The final catalytic composite will contain combined chloride, calculated as the element, in an amount of from about 0.75% to about 1.5% by weight, which combined chloride is the sole halogen component of the catalytic composite. In addition to possessing an unusual degree of activity While effecting the reforming of hydrocarbons and mixtures of hydrocarbons, particularly those boiling at a temperature above the normal gasoline boiling range, the all-chloride catalyst, prepared as hereinabove set forth, appears to be of a physical and/or chemical structure such that the greater proportion of the combined chloride tends to remain composited with the catalyst during processing, which effect is not experienced with the catalytic composites described within the prior art.

The following examples are given to illustrate the method of preparing the catalyst for use in the process of the present invention, and to indicate the benefits afforded a process for reforming of hydrocarbon charge stocks containing hydrocarbons boiling above the normal gasoline boiling range through the utilization of such catalytic composites. It is not intended that the catalytic reforming process of the present invention be unduly limited to the operating conditions employed within the examples. The reaction zone, or zones, is maintained at a temperature within the range of from about 850 F. to about 1050 F., and under an imposed pressure within the range of from about 450 to about 1500 pounds per square inch or more. The liquid hourly space velocity, defined as volumes of liquid hydrocarbon charge per volume of catalyst disposed within the reaction zone, will generally lie within the range of from about 0.1 to about 10.0. Lower liquid hourly space velocities are preferred, primarily for the purpose of increasing the conversion per pass, and lie within the range of from about 0.5 to an upper limit of about 5.0. The resulting reformed product is passed, in its entirety, into a separating zone for the purpose of removing a hydrogen-rich gaseous phase which is recycled to combine with the original liquid hydrocarbon charge. This gaseous recycle is of an amount such that the mol ratio of hydrogen to hydrocarbons, entering the first reaction zone, is within the range of from about 2:1 to about 20:1 or more. In addition to the operating conditions, it is understood that the present invention is not to be unduly limited, 'beyond the scope and spirit of the appended claims, to the various reagents or concentrations thereof employed within these examples, or to the precise hydrocarbon charge stocks utilized.

EXAMPLE I A catalyst was prepared utilizing -inch alumina spheres, manufactured in accordance with US, Patent No. 2,620,314 issued to James Hoekstra, and containing 0.35% by weight of combined chloride. The spheres were intimately commingled with a sufficient quantity of an aqueous solution of hydrogen fluoride to combine therewith about 0.35% by weight of combined fluoride. The spheres were then dried and subjected to a single calcination procedure at a temperature of about 900 F. The calcined spheres were impregnated with an aqueous solution of chloroplatinic acid in an amount to yield a final catalyst containing 0.75% by weight of platinum, calculated as the element thereof. The impregnated spheres were dried at a temperature of about 300 F., and thereafter calcined, in an atmosphere of air, at a temperature of about 900 F., for a period of about 2 hours until such time as the volatile matter content of the catalyst was below a level of about 2.0% by weight. This catalyst is an example of the present-day, reformingtype catalysts containing platinum and combined halogen. In the following discussion and tables, this catalyst is designated as catalyst A, and is employed for the purpose of evaluating the all-chloride catalyst prepared in the particular manner as hereinafter set forth.

A second catalyst, hereinafter designated as catalyst B, was prepared by forming an aluminum chloride hydrosol into -inch spheres by the oil drop method. The alumina spheres Were dried at a temperature of about 400 F., and thereafter calcined, in an atmosphere of air, for a period of one hour at a temperature of 950 F. The calcination temperature was then increased to a level of 1265 F., and the calcination procedure continued at the elevated temperature for a period of two hours, until the volatile matter content of the alumina spheres had decreased to a level of 1.98% by weight. The calcined alumina spheres were then commingled, in a rotating evaporator, with water, hydrochloric acid, and suflicient chloroplatinic acid to composite 0.375% by weight of platinum therewith. On the basis of about 600 pounds of the -inch calcined alumina spheres, 136 gallons of water and 34.6 pounds of a 34.6% by weight of hydrochloric acid were added to the rotating evaporator. The alumina spheres were dried within the rotating evaporator at a steam pressure of about 50 pounds, for a period of six hours. The dried spheres were then subjected to high-temperature calcination, or oxidation, at a temperature of 550 F., for a period of one hour until the volatile matter content was 4.5% by weight. The temperature was then increased to a level of 932 F., and further calcination was effected for a period of two hours, until the volatile matter content had decreased to a level of 1.7% by weight. As indicated in Table I, this catalyst was fluoride-free, and contained 0.375% by weight of platinum and 0.95% by weight of combined chloride, calculated as the element thereof.

A third catalyst, hereinafter designated as catalyst C, was prepared in accordance with the method hereinabove set forth in regard to catalyst B, with the exception that sufiicient chloroplatinic acid was employed during the impregnating technique to composite 0.750% by weight of platinum therewith. This catalyst was also fluoride-free, containing 0.95% by weight of combined chloride as the sole halogen component thereof.

The three catalyst portions were then subjected, individually, to a particular activity-stability test which comprises passing a standard hydrocarbon charge stock, having a boiling range of about 200 F. to about 400 F. It is recognized that this charge stock boils entirely within the gasoline boiling range, or below a temperature of about 400 F. However, this example and that immediately following, is presented to illustrate the unexpected degree of activity and stability of the catalyst of the present invention when compared to present-day reforming catalysts employed primarily with such charge stocks. A later example is presented to show the unexpected results obtained when the charge stock contains hydrocarbons boiling above a temperature of about 400 F.

l l The standard activity test charge stock was passed through the catalyst at a liquid hourly space velocity of 2.0, in admixture with hydrogen present in a mol ratio, of hydrogen to hydrocarbon, of 14:1, for a period of 14 hours. The reaction zones were maintained at a temperature of 932 F., and were under an imposed pressure of 500 pounds per square inch. The liquid product, from each reaction zone, over the entire 14-hour period of the test, was analyzed for its octane rating (P-l clear). The results of this standard relative activity test procedure are given in the following Table I.

Table l.-Standard relative activity test results Catalyst Designation A B Analysis, Wt. percent:

Platinum 0. 750 O. 375 0. 750 Fluoride 0 0 Chloride 0. 350 0.95 0. 95 Total Halogen 0.700 0. 95 0. 95 Octane Rating of Product, F-1 Clean- 94. 9 96. 4 96. 8 Excess Receiver Gas, s.c.f./bb1 828 858 918 Excess Debutanizer Gas, s.c.t./bbl 447 462 444 Total Excess Gas, s.e.i./bbl 1,275 1,320 1, 362 Debutanizer Gas Ratio 351 0.350 0.326 Activity Ratings:

Debutanizer Overhead:

At same Octane 100 98 93 At same Total Gas 100 98 89 Octane Number, Space Velocity 100 112 119 For the purpose of obtaining a clear understanding of the data, several definitions of the terms employed in Table I are given below:

(1) The excess receiver gas is that quantity of gas in excess of the amount required to maintain the desired pressure within the reaction zone. Analyses have indicated that this gas is, for all practical purposes, substantially pure hydrogen (approximately 9095 mol percent throughout the 14-hour period of the standard activity test).

(2) The excess debutanizer gas is that gaseous product which is composed primarily of light parafiins, methane, ethane, propane and butane, along with some hydrogen, and results primarily from the hydrocracking reactions being effected within the reaction zone.

(3) The debutanizer gas ratio is the ratio of excess debutanizer gas to the total excess gas, standard cubic feet per barrel, and is indicative of the relative yield of desirable liquid product within the effiuent from the reaction zone; it is, to a certain extent, an indication of the relative stability of the catalyst. The lower the debutantizer gas ratio, the more active the catalyst for the purpose of eifecting the reforming of hydrocarbons, and greater is the stability of the catalyst.

(4) The activity ratings are employed on a comparative basis with respect to the standard catalyst, catalyst A; they are first compared at identical octane ratings and total excess gas production, and at equivalent liquid hourly space velocities. In the latter instance, the larger the number, the more active the catalyst; in the former instances, the smaller the number, the greater the yield of high-octane product.

The data given in Table I clearly indicate the benefits afiorded the catalytic reforming of hydrocarbons through the utilization of the catalyst prepared in accordance with the particular manner hereinbefore set forth. Both of the fluoride-free, all-chloride catalysts, B and C, resulted in a lesser quantity of excess debutanizer gas than the standard catalyst, when compared at the same octane rating and at the same total excess gas production. Similarly, these catalysts indicated greater than increase in space velocity activity. Upon comparing catalyst C with catalyst A, both of which contain the same quantity of platinum, it is seen that catalyst C resulted in 7% less excess debutanizer gas, compared at the same octane rating, and exhibited a significantly lower debutanizer gas ratio, while at the same time producing a liquid product having a significantly greater octane rating. It is further significant that catalyst C contained approximately 0.25% by weight additional halogen which, according to expectations when considering the prior art teachings, should have resulted in a greater degree of hydrocracking, in turn resulting in a higher debutanizer gas ratio; unexpectedly, the activity ratings, relative to excess debutanizer gas production, indicate the contrary.

The three catalysts, hereinbefore described, were subjected, individually, to a second standard test procedure designed to evaluate the stability of the catalyst over an extended period of time. This secondary evaluation test procedure involves the utilization of a light naphtha having a boiling range from about 160 F. to about 260 F., and is effected at operating conditions specifically designed to induce instability to the operation. The catalyst is maintained at a pressure of 300 pounds per square inch and the charge is passed therethrough at a liquid hourly space velocity of 1.5, in the presence of hydrogen in an amount to yield a mol ratio of 12:1. The test procedure is effected for a period of approximately 150 hours or more, varying the operating temperature to maintain an octane rating of 100.0 (F-l clear) on the pentanes and heavier portion of the normally liquid product efiiuent. The various results are plotted against time, and the relative activity and stability is determined by comparing the data to that resulting from the reference catalyst. The relative stability of the catalyst is de termined by comparing the slope of the various plots at hours, to the slope of the reference catalyst at 100 hours. The data resulting from the extended stability test are given in the following Table II:

Table II.Extendea' stability test, stability 100 hours Catalyst Designation .A. B 0

Block Temperature, F 1, 022 1, 000 996 Excess Receiver Gas, s.c.t./bbl 1, 182 1, 266 Excess Debutanizer Gas, s.c.l./bbl 461 423 357 Total Excess Gas, s.c.i./bbl 1, 571 1, 605 1,623 Debutanizer Gas Ratio 0.293 0. 264 0.220 Yield, Pentanes and Heavier, Vol. percen 57. 2 59.1 61. 8

EXAMPLE II A second extended stability test procedure was performed, comparing the standard platinum-chloride-iiuoride catalyst with a catalyst containing 0.81% of chlorine by weight, as the sole halogen component thereof. This catalyst is designated in the following table as catalyst D, and differs from catalyst C only in the slightly lower concentration of combined chloride. The extended stability operation was carried out for a total period of hours at a liquid hourly space velocity of 1.5, and an operating pressure of 300 pounds per square inch, at a hydrogen to hydrocarbon mol ratio of about 7.5. The charge stock was a light naphtha having a boiling range from 168 F. to 275 F., and contained 76.0% parafiins,

13 17 .0% naphthenes and 7.0% aromatics, on a volumetric basis. The operating temperature was subjected to change, throughout the total period of 185 hours, in order to maintain an octane rating, on the debutanized liquid product, of 100.0 (F-1 clear).

The two catalysts A and D, were compared during the initial portion of the extended stability test, that is, at 41 hours, and at the end of the extended stability test, at 185 hours. a The data obtained are presented in the following Table IH, and indicate the benefits afforded the catalytic reforming of hydrocarbons, utilizing an allchloride catalyst free from combined fluoride.

Table III.Extended stability test-185 hours 100.0

F-1 clear Catalyst Designation A D A D Period Duration, Hours -1 41 41 185 185 Block Temperature, F 1, 025 1, 020 1, 036 1,016 Severity Difierentia], F./Hr 0.118 0.007 Excess Receiver Gas, s.c.f./bbl 1, 288 1, 378 1,008 1, 204 Excess Debutanizer Gas, s.c.f./hb1- 406 352 516 425 Total Excess Gas, s.c.f./bbl 1, 694 1, 730 1, 524. 1, 629 Debutanizer Gas Ratio .240 .204 .336 261 Yield, Pentanes and Hea r, Vol.

percent 60. 1 61. 8 55. 2 59.0 Carbon Deposition, Wt. percent 5. 39 3. 59

The severity differential was obtained by computing the average slope of the temperature-time plot over the entire period of operation. This differential is indicative of the prospective catalyst life to be expected in terms of the stability of the catalyst.

From the foregoing data, it is readily ascertained that the all-chloride catalyst possesses substantially increased activity and stability. This is indicated by the severity differential of 0.007 F. per hour for the all-chloride catalyst, as compared to a temperature differential of 0.118 F. per hour. Furthermore, the volumetric yield of pentanes and heavier hydrocarbons decrease to the extent of about 5.0%, and only 2.8% for the all-chloride catalyst. In addition, and of greater significance, is the '"fact that the all-chloride catalyst indicated a carbon deposition, as a result of the extended period of operation, of only 3.59% by weight, whereas the standard catalyst exhibited a carbon deposition of 5.39% by weight.

Other pertinent properties of this charge stock are given in the following Table IV. Of the 10.1% aromatics and olefins, boiling at a temperature above the normal gasoline boiling range, 0.26% by volume (based upon the total charge stock) were alkylnaphthalenes. As hereinafter indicated in greater detail, the utilization of the all-chloride catalyst for the reforming of this particular hydrocarbon charge stock, results in a net production of hydrocarbons boiling below the initial boiling point of 220 F., and further reforms the heavier portion of the charge stock to increase the yield of alkylnaphthalenes.

Table I V.Chizrge stock properties Gravity, API F 52.0 Specific gravity 60 F. 0.7711 ASTM 100 ML. distillation (D86-56):

Initial boiling point 220 5% 242 10% 254 30% 282 50% 310 348 90% 394 412 End boiling point 445 Sulfur, wt. percent 0.012 Total nitrogen, ppm. 0.14 Hydrocarbon type analysis, vol. percent:

Aromatics 9.6

Olefins 0.5 Parafifins plus naphthenes 89.9

This unexpected result, obtained through the utilization of the catalyst of the present invention, and under selective operation conditions, is readily recognized by one possessing skill within the art of petroleum processing as an additional advantage to the over-all process. The resulting alkylnaphthalenes are separated from the total reformed product effluent, and thereafter subjected to a particular hydrodealkylation process to produce a substantially pure naphthalene concentrate, and the saturated hydrocarbon corresponding to the alkyl group which is removed from the naphthalene molecule.

Table V.-0perating conditions Reactor Block Temperature, F Average Catalyst BedTemperature, F. p.s.1.g

Liquid Hourly Space Velocity Reactor Pressure,

Recycle Gas/Oil Ratio Recycle Gas Hydrogen, M01 percent.-.

Vent Gas Rates, s.c.f./b.:

Separator Gas Debutanizer Gas Total Period Designation 1 2 3 4 5 6 7 8 Debutanizer Gas Ratio Other comparisons may be made from the data presented in Table III, and these comparisons will indicate the greater degree of stability and activity possessed by the all-chloride catalyst.

EXAMPLE III A total of eight test periods was performed, varying the catalyst bed temperature, the reaction zone pressure and the recycle hydrogen to hydrocarbon mol ratio. The various operating conditions for these eight periods are given in Table V.

It should be noted that the debutanizer gas ratios, previously discussed with respect to Example I, were consistently low throughout the entire period of operation, and compare favorably with the debutanizer gas ratios set forth in the previous examples, notwithstanding that the charge stock contained hydrocarbons boiling at a temperature above the normal gasoline boiling range. This is especially significant in regard to Period No. 8, during which the reaction zone pressure was 500 pounds per square inch, the recycle gas to oil ratio had been de- 15 creased to 12.0, with a resulting lower average catalyst bed temperature of 920 F. The debutanizer gas ratio for this eighth period was only 0.160.

The total liquid product efiiuent was passed into a highpressure separator, operating at substantially the same aromatic hydrocarbons boiling in excess of the normal pressure as the reaction zone, and at a temperature of gasoline boiling range; as indicated in the yields for about 80 F., for the purpose of removing a hydrogen Period No. 8, there was an increase in alkylnaphthalenes rich gaseous phase which was recycled to combine with to 4.6 volume percent (based upon the original charge tothe original hydrocarbon charge, prior to passing the same the process), a 71.7 volumetric percent yield of gasoline into the reaction zone. The normally liquid hydrocarboiling range hydrocarbons having the octane rating of bons from the high-pressure separator were then sub- 95.8, and 6.3% by volume of isoand normal butanes jected to precise laboratory distillation in a multi-plate which find value either as gasoline blending components fractionating column, for the purpose of separating a (to increase the Reid vapor pressure), or as subsequent gasoline fraction from the total product at precise cut charge stock to a unit specifically designed to effect the point of 392 F. Various product inspections, including a'lkylation thereof.

the octane rating and hydrocarbon-type analysis of the gasoline fraction, and the naphtha bottoms fraction (boil ing at a temperature in excess of 392 F.) are given in the following Table VI. As indicated in Table VI, the

naphtha bottoms fraction was virtually 100% aromatic,

containing only a trace of olefinic hydrocarbons. In regard to Period No. 8, the gasoline fraction, having an octane rating, F-l clear, of 95.8, consisted of 61.4%

Various liquid and light paraifinic hydrocarbon yields are presented in the following Table VII for these eight test periods. It is immediately ascertained that there has been an increase in the quantity of polynuclear Other evaluations of the data presented in Tables V, VI and VII may be made for the purpose of further indicating the benefits now afforded to the process of catalytically reforming a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above the normal gasoline boiling range. Similar advantages are realized when the charge stock is considerably heavier, for example, a kerosene fraction, having an initial boil- Table VI.-Pr0duct inspections Period Designation 1 2 3 4 5 6 7 8 Gasoline Fraction, IBP392 F.:

Gravity, API at F 50. 3 49. 4 47. 7 43. 7 48.0 47. 4 48. 0 46. 7 Initial Boiling Point, F 140 136 134 117 132 129 130 134 5 180 166 165 148 162 158 156 168 198 185 182 168 180 176 173 186 236 230 228 228 230 226 219 235 268 264 267 275 268 267 261 273 296 295 298 302 298 208 295 302 331 327 334 338 333 333 330 336 95% 345 340 348 354 348 348 345 349 End Boiling Point 372 375 380 378 362 380 372 368 Reid Vapor Pressure, Lbs 3.0 3. 3 3. 7 5. 8 3. 8 3. 6 4. 2 3. 3 Octane Rating, .F-l Clear 86. 1 90. 4 94. 6 100.0 94. 5 96.0 95. 6 95.8 Hydrocarbon Type Analysis, Vol.

Percent of 08+:

Aromatics 47. 6 52. 5 59. 7 76. 7 57. 3 61. 8 61. 5 61. 4 Olefms 0.7 0. 7 0.4 0.9 0.6 0.7 1.0 Paraifins Plus Naphthenes 52. 4 46 8 39. 6 22. 9 41.8 37. 6 37 8 37. 6 Naphtha Bottoms Fraction, 392 F.+:

Gravity, API at 60 F 21. 5 20. 0 17. 4 11.2 17. 7 16. 9 16. 6 16. 7 Octane Rating, F-l Clear 111.3 110. 5 111.6 108. 3 116.5 112. 9 112. 7 Hydrocarbon Type Analysis, Vol.

Percent:

Aromatics 94. 3 97. 0 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Olefins 0.7 0. 6 TR TR T T TR Parafiins Plus Naphthenes 5.0 2. 4

Table VII .-Pr0duct yields Period Designation 1 2 3 4 5 6 7 8 Light Parafiinic Hydrocarbons, s.c.f.lb.:

Methane 118 137 161 212 159 154 123 119 Ethane- 82 101 146 97 98 107 89 Propane 78 94 112 143 119 125 133 98 Total 261 313 374 501 375 377 363 306 Liquid Yields, Gasoline Fraction, Vol.

Percent:

ISO-Butane 1. 8 2- 3 2- 7 3. 3 2. 8 3. 0 3. 2 2. 5 t 3. 5 4. 0 4. 5 4. 6 4. 6 5. 0 5. 4 3. 8 Iso-Pentane- 2. 9 3. 1 3. 9 4. 5 3. 8 4. 0 4. 6 3. 5 N-Pentane 1. 9 2. 6 2. 4 3. 2 2. 5 2. 6 3. 0 2. 2 Hexanes to 392 F 73. 4 69. 3 66. 5 61. 2 65.0 64. 9 64. 4 66.0 Pentanes to 392 F l 78. 2 75.0 72. 8 68. 9 71. 3 71. 5 71.0 71. 7 Butanes to 392 F 83. 5 81. 3 80. 0 76. 8 78. 7 79. 5 S0. 6 78.0 Liquid Yield, Naphtha Bottoms, Vol.

Percent 7. 5 7. 9 6. 9 5. 3 7. 8 7. 0 7. 0 9. 4 Alkylnaphthalenes 5 2. 9 3. 0 3. 7 3. 2 3. 1 3. 3 4. 6

by volume of aromatic hydrocarbons. When considered in conjunction with the extremely low debutanizcr gas ratio set forth in Table V, the production of the gasoline fraction of this nature, as well as a naphtha bottoms fraction virtually 100% aromatic, clearly indicates the totally unexpected beneficial results obtained through the utilization of the catalyst and process of the present in vention.

the remaining 32% by volume boiling above the normal gasoline boiling range, and containing in excess of about 90.0% by volume of aromatic hydrocarbons.

The foregoing examples clearly illustrate the catalytic reforming process of the present invention, and indicate the benefits to be afforded through the utilization thereof. It is now possible to reform catalytically those hydrocarbon charge stocks containing hydrocarbons boiling above the normal gasoline boiling range, without experiencing comparatively rapid catalyst deactivation as well as high yield loss due to excessive, non-selective hydrocracking of the heavier portion of the charge stock.

I claim as my invention:

1. A process for the conversion of a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above about 400 F. which comprises reacting said charge stock with hydrogen in contact with a fluoridefree catalytic composite of a platinum-group metallic component, a refractory inorganic oxide and combined chloride in an amount above about 0.75% but below 1.5% by weight, calculated as elemental chlorine, at conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge, and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F., said catalytic composite having been initially calcined at a temperature of from about 400 F. to about 600 F. for at least one hour until the volatile matter content thereof has been decreased to below about 5.0% by weight and then further calcined at a temperature of from about 700 F. to about 1000 F. for an additional period of at least one hour until the volatile matter content has been decreased to below about 2.0% by weight.

2. A process for the conversion of a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above about 400 P. which comprises reacting said charge stock with hydrogen in contact with a fluoridefree catalytic composite of a platinum-group metallic component, a refractory inorganic oxide and combined chloride in an amount above about 0.75% but below 1.5 by weight, calculated as elemental chlorine, at conditions of a temperature Within the range of from about 850 F. to about 1050 F., a pressure of from about 450 to about 1500 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10.0, said conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge, and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F., said catalytic composite having been initially calcined at a temperature of from about 400 F. to about 600 F. for at least one hour until the volatile matter content thereof has been decreased to below about 5.0% by weight and then further calcined at a temperature of from about 700 F. to about 1000 F. for an additional period of at least one hour until the volatile matter content has been decreased to below about 2.0% by weight.

3. The process of claim 2 further characterized in that said platinum-group metallic component is platinum.

4. A process for the conversion of a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above about 400 F. which comprises reacting said charge stock with hydrogen in contact with a fluoridefree catalytic composite of from about 0.01% to about 5.0% by Weight of platinum, alumina and combined chloride in an amount above about 0.75% but below 1.5% by weight, calculated as elemental chlorine, at conditions of a temperature within the range of from about 850 F. to about 1050 F., a pressure of from about 450 to about 1500 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10.0, said conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge, and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F., said catalytic composite having been initially calcined at a temperature of from about 400 F. to about 600 F. for at least one hour until the volatile matter content thereof has been decreased to below about 5.0% by weight and then further calcined at a temperature of from about 700 F. to about 1000 F. for an additional period of at least one hour until the volatile matter content has been decreased to below about 2.0% by weight.

5. The process of claim 4 further characterized in that said pressure is within the range of from about 450 to about 900 pounds per square inch.

6. A process for the conversion of a hydrocarbon charge stock containing hydrocarbons boiling at a temperature above about 400 F. which comprises reacting said charge stock with hydrogen present in a mol ratio of hydrogen to hydrocarbon of from about 2:1 to about 20:1, and in contact with a fluoride-free catalytic composite of alumina, from about 0.01% to about 5.0% by Weight of platinum and combined chloride in an amount above about 0.75% but below 1.5% by weight, calculated as elemental chlorine, at reforming conditions of a temperature within the range of from about 850 F. to about 1050 F., a pressure of from about 450 to about 900 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10.0, said conditions selected to produce a net volumetric yield of hydrocarbons boiling at a temperature below the initial boiling point of said hydrocarbon charge and a net volumetric yield of polynuclear aromatic hydrocarbons boiling at a temperature above about 400 F., said catalytic composite having been initially calcined at a temperature of from about 400 F. to about 600 F. for at least one hour until the volatile matter content thereof has been decreased to below about 5.0% by weight and then further calcined at a temperature of from about 700 F. to about 1000 F. for an additional period of at least one hour until the volatile matter content has been decreased to below about 2.0% by weight.

References Cited by the Examiner UNITED STATES PATENTS 2,479,110 8/49 Haensel 208139 2,631,136 3/53 Haensel 252--442 2,780,661 2/57 Hemminger et al 208127 3,012,961 12/61 Weisz 208-66 FOREIGN PATENTS 712,440 1 5 2 Great Britain.

ALPHONSO D. SULLIVAN, Primary Examiner. 

1. A PROCESS FOR THE CONVERSION OF A HYDROCARBON CHARGE STOCK CONTAINING HYDROCARBONS BOILING AT A TEMPERATURE ABOVE ABOUT 400*F. WHICH COMPRISES REACTING SAID CHARGE STOCK WITH HYDROGEN IN CONTACT WITH A FLUORIDEFREE CATALYTIC COMPOSITE OF A PLATIMUM-GROUP METALLIC COMPONENT, A REFRACTORY INORGANIC OXIDE AND COMBINED CHLORIDE IN AN AMOUNT ABOVE ABOUT 0.75% BUT BELOW 1.5% BY WEIGHT, CALCULATED AS ELEMENTALCHLORINE, AT CONDITIONS SELECTED TO PRODUCE A NET VOLUMETRIC YIELD OF HYDROCARBONS BOILING AT A TEMPERATURE BELOW THE INITIAL BOILING POINT OF SAID HYDROCARBON CHARGE, AND A NET VOLUMETRIC YIELD OF POLYNUCLEAR AROMATIC HYDROCARBONS BOILING AT A TEMPERATURE ABOVE ABOUT 400*F., SAID CATALYTIC COMPOSITE HAVING BEEN INITIALLY CALCINED AT A TEMPERATURE OF FROM ABOUT 400*F. TO ABOUT 600*F. FOR AT LEAST ONE HOUR UNTIL THE VOLATILE MATTER CONTENT THEREOF HAS BEEN DECREASED TO BELOW ABOUT 5.0% BY WEIGHT AND THEN FURTHER CALCINED AT A TEMPERATURE OF FROM ABOUT 700*F. TO ABOUT 1000*F. FOR AN ADDITIONAL PERIOD OF AT LEAST ONE HOUR UNTIL THE VOLATILE MATTER CONTENT HAS BEEN DECREASED TO BELOW ABOUT 2.0% BY WEIGHT. 